U.S. patent number 9,954,180 [Application Number 13/816,407] was granted by the patent office on 2018-04-24 for bicarbazole compounds for oleds.
This patent grant is currently assigned to Universal Display Corporation. The grantee listed for this patent is Ming-Cheng Kuo, Raymond Kwong, Ken-Tsung Wong, Chuanjun Xia. Invention is credited to Ming-Cheng Kuo, Raymond Kwong, Ken-Tsung Wong, Chuanjun Xia.
United States Patent |
9,954,180 |
Xia , et al. |
April 24, 2018 |
Bicarbazole compounds for OLEDs
Abstract
Novel organic compounds comprising a bicarbazole core are
provided. In particular, the compounds has a 3,3'-bicarbazole core
substituted at the 9-position with a triazine or pyrimidine. The
compounds may be used in organic light emitting devices to provide
devices having improved efficiency and improved lifetime.
Inventors: |
Xia; Chuanjun (Lawrenceville,
NJ), Kwong; Raymond (Plainsboro, NJ), Wong; Ken-Tsung
(Tapei County, TW), Kuo; Ming-Cheng (Taichung County,
TW) |
Applicant: |
Name |
City |
State |
Country |
Type |
Xia; Chuanjun
Kwong; Raymond
Wong; Ken-Tsung
Kuo; Ming-Cheng |
Lawrenceville
Plainsboro
Tapei County
Taichung County |
NJ
NJ
N/A
N/A |
US
US
TW
TW |
|
|
Assignee: |
Universal Display Corporation
(Ewing, NJ)
|
Family
ID: |
42805990 |
Appl.
No.: |
13/816,407 |
Filed: |
August 20, 2010 |
PCT
Filed: |
August 20, 2010 |
PCT No.: |
PCT/US2010/046218 |
371(c)(1),(2),(4) Date: |
February 11, 2013 |
PCT
Pub. No.: |
WO2012/023947 |
PCT
Pub. Date: |
February 23, 2012 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20130140549 A1 |
Jun 6, 2013 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L
51/0072 (20130101); C07D 405/14 (20130101); C07D
403/14 (20130101); H01L 51/0067 (20130101); C07D
409/14 (20130101); C07D 401/14 (20130101); H01L
51/5016 (20130101); H01L 51/0085 (20130101) |
Current International
Class: |
H01L
51/50 (20060101); H01L 51/00 (20060101); C07D
401/14 (20060101); C07D 403/14 (20060101); C07D
405/14 (20060101); C07D 409/14 (20060101) |
Field of
Search: |
;544/180,194,211,212
;548/440 ;257/40,E51.05,88-104,E51.001-E51.052
;428/690,917,505,506,691 ;427/58,66 ;313/500-512
;252/301.16-301.35 |
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|
Primary Examiner: Bohaty; Andrew K
Assistant Examiner: Kershner; Dylan C
Attorney, Agent or Firm: Duane Morris LLP
Claims
The invention claimed is:
1. A compound having the formula: ##STR00371## wherein R.sub.1 and
R.sub.4 may represent mono, di, tri, or tetra substitutions;
wherein R.sub.2 and R.sub.3 may represent mono, di, or tri
substitutions; wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are
independently selected from the group consisting of hydrogen,
alkyl, alkoxy, amino, alkenyl, alkynyl, aryl and heteroaryl;
wherein A.sub.1 and Ar.sub.2 are independently selected from aryl
or heteroaryl; wherein X is C or N; and wherein at least one of the
following it true: (1) Ar.sub.3 is independently selected from the
group consisting of fluorene, dibenzofuran, dibenzothiophene, and
triphenylene, and at least one of Ar.sub.1, Ar.sub.2, and Ar.sub.3
is substituted with a substituent selected from the group
consisting of alkyl, alkoxy, alkenyl, alkynyl, aryl and heteroaryl,
wherein the substituent is not an aryl or heteroaryl fused directly
to Ar.sub.1, Ar.sub.2, or Ar.sub.3; and (2) Ar.sub.3 is selected
from the group consisting of fluorene, dibenzofuran, and
dibenzothiophene.
2. The compound of claim 1, wherein at least one of Ar.sub.1,
Ar.sub.2, and Ar.sub.3 is substituted with a substituent selected
from the group consisting of alkyl, alkoxy, alkenyl, alkynyl, aryl
and heteroaryl, wherein the substituent is not an aryl or
heteroaryl fused directly to A.sub.1, Ar.sub.2, or Ar.sub.3.
3. The compound of claim 1, wherein A.sub.1 and Ar.sub.2 are
independently selected from the group consisting of phenyl,
pyridine, naphthalene, biphenyl, terphenyl, fluorene, dibenzofuran,
dibenzothiophene, phenanthrene, and triphenylene; and wherein at
least one of A.sub.1, Ar.sub.2, and Ar.sub.3 is further substituted
with a substituent selected from the group consisting of alkyl,
alkoxy, alkenyl, alkynyl, aryl and heteroaryl, wherein the
substituent is not an aryl or heteroaryl fused directly to A.sub.1,
Ar.sub.2, or Ar.sub.3.
4. The compound of claim 1, wherein A.sub.1 and Ar.sub.2 are
independently selected from the group consisting of phenyl,
pyridine, and naphthalene.
5. The compound of claim 1, wherein Ar.sub.3 is selected from the
group consisting of fluorene, dibenzofuran, and
dibenzothiophene.
6. The compound of claim 1, wherein R.sub.1, R.sub.2, R.sub.3, and
R.sub.4 are hydrogen.
7. A first device comprising an organic light emitting device,
further comprising: an anode; a cathode; and an organic layer,
disposed between the anode and the cathode, wherein the organic
layer comprises a compound having the formula: ##STR00372## wherein
R.sub.1 and R.sub.4 may represent mono, di, tri, or tetra
substitutions; wherein R.sub.2 and R.sub.3 may represent mono, di,
or tri substitutions; wherein R.sub.1, R.sub.2, R.sub.3, and
R.sub.4 are independently selected from the group consisting of
hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aryl and
heteroaryl; wherein Ar.sub.1 and Ar.sub.2 are independently
selected from aryl or heteroaryl; wherein X is C or N; and wherein
at least one of the following it true: (1) Ar.sub.3 is
independently selected from the group consisting of fluorene,
dibenzofuran, dibenzothiophene, and triphenylene, and at least one
of Ar.sub.1, Ar.sub.2, and Ar.sub.3 is substituted with a
substituent selected from the group consisting of alkyl, alkoxy,
alkenyl, alkynyl, aryl and heteroaryl, wherein the substituent is
not an aryl or heteroaryl fused directly to Ar.sub.1, Ar.sub.2, or
Ar.sub.3; and (2) Ar.sub.3 is selected from the group consisting of
fluorene, dibenzofuran, and dibenzothiophene.
8. The device of claim 7, wherein at least one of Ar.sub.1,
Ar.sub.2, and Ar.sub.3 is substituted with a substituent selected
from the group consisting of alkyl, alkoxy, alkenyl, alkynyl, aryl
and heteroaryl, wherein the substituent is not an aryl or
heteroaryl fused directly to A.sub.1, Ar.sub.2, or Ar.sub.3.
9. The device of claim 7, wherein A.sub.1 and Ar.sub.2 are
independently selected from the group consisting of phenyl,
pyridine, naphthalene, biphenyl, terphenyl, fluorene, dibenzofuran,
dibenzothiophene, phenanthrene, and triphenylene; and wherein at
least one of A.sub.1, Ar.sub.2, and Ar.sub.3 is further substituted
with a substituent selected from the group consisting of alkyl,
alkoxy, alkenyl, alkynyl, aryl and heteroaryl, wherein the
substituent is not an aryl or heteroaryl fused directly to A.sub.1,
Ar.sub.2, or Ar.sub.3.
10. The device of claim 7, wherein A.sub.1 and Ar.sub.2 are
independently selected from the group consisting of phenyl,
pyridine, and naphthalene.
11. The device of claim 7, wherein Ar.sub.3 is selected from the
group consisting of fluorene, dibenzofuran, and
dibenzothiophene.
12. The device of claim 7, wherein R.sub.1, R.sub.2, R.sub.3, and
R.sub.4 are hydrogen.
13. The device of claim 7, wherein the organic layer is deposited
using solution processing.
14. The device of claim 7, wherein the organic layer is an emissive
layer and the compound having Formula I is a host.
15. The device of claim 14, wherein the organic layer further
comprises an emissive dopant having the structure: ##STR00373##
##STR00374## ##STR00375## ##STR00376## ##STR00377## ##STR00378##
##STR00379## ##STR00380## ##STR00381## ##STR00382##
16. The device of claim 7, wherein the first device is a consumer
product.
17. The device of claim 7, wherein the first device is an organic
light emitting device.
18. The compound of claim 1, wherein the compound is selected from
the group consisting of: ##STR00383## ##STR00384## ##STR00385##
##STR00386## ##STR00387## ##STR00388## ##STR00389## ##STR00390##
##STR00391## ##STR00392## ##STR00393## ##STR00394## ##STR00395##
##STR00396## ##STR00397## ##STR00398## ##STR00399## ##STR00400##
##STR00401## ##STR00402## ##STR00403## ##STR00404## ##STR00405##
##STR00406##
19. The device of claim 7, wherein the compound is selected from
the group consisting of: ##STR00407## ##STR00408## ##STR00409##
##STR00410## ##STR00411## ##STR00412## ##STR00413## ##STR00414##
##STR00415## ##STR00416## ##STR00417## ##STR00418## ##STR00419##
##STR00420## ##STR00421## ##STR00422## ##STR00423## ##STR00424##
##STR00425## ##STR00426## ##STR00427## ##STR00428## ##STR00429##
##STR00430##
20. The compound of claim 1, wherein the compound is selected from
the group consisting of: ##STR00431## ##STR00432## ##STR00433##
##STR00434## ##STR00435## ##STR00436## ##STR00437## ##STR00438##
##STR00439## ##STR00440## ##STR00441## ##STR00442## ##STR00443##
##STR00444## ##STR00445## ##STR00446## ##STR00447## ##STR00448##
##STR00449## ##STR00450## ##STR00451## ##STR00452## ##STR00453##
##STR00454##
Description
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a U.S. national phase application filed under
35 U.S.C. .sctn. 371 of International Application No.:
PCT/US2010/046218, which was filed on Aug. 20, 2010.
The claimed invention was made by, on behalf of, and/or in
connection with one or more of the following parties to a joint
university corporation research agreement: Regents of the
University of Michigan, Princeton University, The University of
Southern California, and the Universal Display Corporation. The
agreement was in effect on and before the date the claimed
invention was made, and the claimed invention was made as a result
of activities undertaken within the scope of the agreement.
FIELD OF THE INVENTION
The present invention relates to organic light emitting devices
(OLEDs). More specifically, the present invention pertains to
phosphorescent organic materials comprising a bicarbazole having a
nitrogen-containing heterocycle at the 9 position.
BACKGROUND
Opto-electronic devices that make use of organic materials are
becoming increasingly desirable for a number of reasons. Many of
the materials used to make such devices are relatively inexpensive,
so organic opto-electronic devices have the potential for cost
advantages over inorganic devices. In addition, the inherent
properties of organic materials, such as their flexibility, may
make them well suited for particular applications such as
fabrication on a flexible substrate. Examples of organic
opto-electronic devices include organic light emitting devices
(OLEDs), organic phototransistors, organic photovoltaic cells, and
organic photodetectors. For OLEDs, the organic materials may have
performance advantages over conventional materials. For example,
the wavelength at which an organic emissive layer emits light may
generally be readily tuned with appropriate dopants.
OLEDs make use of thin organic films that emit light when voltage
is applied across the device. OLEDs are becoming an increasingly
interesting technology for use in applications such as flat panel
displays, illumination, and backlighting. Several OLED materials
and configurations are described in U.S. Pat. Nos. 5,844,363,
6,303,238, and 5,707,745, which are incorporated herein by
reference in their entirety.
One application for phosphorescent emissive molecules is a full
color display. Industry standards for such a display call for
pixels adapted to emit particular colors, referred to as
"saturated" colors. In particular, these standards call for
saturated red, green, and blue pixels. Color may be measured using
CIE coordinates, which are well known to the art.
One example of a green emissive molecule is tris(2-phenylpyridine)
iridium, denoted Ir(ppy).sub.3, which has the structure:
##STR00001##
In this, and later figures herein, we depict the dative bond from
nitrogen to metal (here, Ir) as a straight line.
As used herein, the term "organic" includes polymeric materials as
well as small molecule organic materials that may be used to
fabricate organic opto-electronic devices. "Small molecule" refers
to any organic material that is not a polymer, and "small
molecules" may actually be quite large. Small molecules may include
repeat units in some circumstances. For example, using a long chain
alkyl group as a substituent does not remove a molecule from the
"small molecule" class. Small molecules may also be incorporated
into polymers, for example as a pendent group on a polymer backbone
or as a part of the backbone. Small molecules may also serve as the
core moiety of a dendrimer, which consists of a series of chemical
shells built on the core moiety. The core moiety of a dendrimer may
be a fluorescent or phosphorescent small molecule emitter. A
dendrimer may be a "small molecule," and it is believed that all
dendrimers currently used in the field of OLEDs are small
molecules.
As used herein, "top" means furthest away from the substrate, while
"bottom" means closest to the substrate. Where a first layer is
described as "disposed over" a second layer, the first layer is
disposed further away from substrate. There may be other layers
between the first and second layer, unless it is specified that the
first layer is "in contact with" the second layer. For example, a
cathode may be described as "disposed over" an anode, even though
there are various organic layers in between.
As used herein, "solution processible" means capable of being
dissolved, dispersed, or transported in and/or deposited from a
liquid medium, either in solution or suspension form.
A ligand may be referred to as "photoactive" when it is believed
that the ligand directly contributes to the photoactive properties
of an emissive material. A ligand may be referred to as "ancillary"
when it is believed that the ligand does not contribute to the
photoactive properties of an emissive material, although an
ancillary ligand may alter the properties of a photoactive
ligand.
As used herein, and as would be generally understood by one skilled
in the art, a first "Highest Occupied Molecular Orbital" (HOMO) or
"Lowest Unoccupied Molecular Orbital" (LUMO) energy level is
"greater than" or "higher than" a second HOMO or LUMO energy level
if the first energy level is closer to the vacuum energy level.
Since ionization potentials (IP) are measured as a negative energy
relative to a vacuum level, a higher HOMO energy level corresponds
to an IP having a smaller absolute value (an IP that is less
negative). Similarly, a higher LUMO energy level corresponds to an
electron affinity (EA) having a smaller absolute value (an EA that
is less negative). On a conventional energy level diagram, with the
vacuum level at the top, the LUMO energy level of a material is
higher than the HOMO energy level of the same material. A "higher"
HOMO or LUMO energy level appears closer to the top of such a
diagram than a "lower" HOMO or LUMO energy level.
As used herein, and as would be generally understood by one skilled
in the art, a first work function is "greater than" or "higher
than" a second work function if the first work function has a
higher absolute value. Because work functions are generally
measured as negative numbers relative to vacuum level, this means
that a "higher" work function is more negative. On a conventional
energy level diagram, with the vacuum level at the top, a "higher"
work function is illustrated as further away from the vacuum level
in the downward direction. Thus, the definitions of HOMO and LUMO
energy levels follow a different convention than work
functions.
More details on OLEDs, and the definitions described above, can be
found in U.S. Pat. No. 7,279,704, which is incorporated herein by
reference in its entirety.
SUMMARY OF THE INVENTION
Compounds comprising a bicarbazole are provided. The compounds have
the formula:
##STR00002##
R.sub.1, R.sub.2, R.sub.3, and R.sub.4 may represent mono, di, tri,
or tetra substitutions. R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are
independently selected from the group consisting of hydrogen,
alkyl, alkoxy, amino, alkenyl, alkynyl, aryl and heteroaryl.
Ar.sub.1, Ar.sub.2, and Ar.sub.3 are independently selected from
aryl or heteroaryl. Ar.sub.1, Ar.sub.2, and Ar.sub.3 may be further
substituted. X is C or N.
In one aspect, Ar.sub.1, Ar.sub.2, and Ar.sub.3 are independently
selected from the group consisting of phenyl, pyridine,
naphthalene, biphenyl, terphenyl, fluorene, dibenzofuran,
dibenzothiophene, phenanthrene, and triphenylene. Ar.sub.1,
Ar.sub.2, and Ar.sub.3 are independently further substituted with a
substituent selected from the group consisting of hydrogen, alkyl,
alkoxy, amino, alkenyl, alkynyl, aryl and heteroaryl, but the
substituent is not an aryl or heteroaryl fused directly to
Ar.sub.1, Ar.sub.2, and Ar.sub.3. Preferably, Ar.sub.1 and Ar.sub.2
are independently selected from the group consisting of phenyl,
pyridine, and naphthalene. Preferably, Ar.sub.3 is selected from
the group consisting of phenyl, biphenyl, dibenzofuran, and
dibenzothiophene.
In another aspect, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are
hydrogen.
Specific examples of compounds comprising bicarbazole are also
provided. In particular, the compound is selected from the group
consisting of:
##STR00003## ##STR00004## ##STR00005## ##STR00006## ##STR00007##
##STR00008## ##STR00009## ##STR00010## ##STR00011## ##STR00012##
##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017##
##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022##
##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027##
##STR00028## ##STR00029## ##STR00030## ##STR00031## ##STR00032##
##STR00033## ##STR00034## ##STR00035## ##STR00036## ##STR00037##
##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042##
##STR00043## ##STR00044## ##STR00045## ##STR00046## ##STR00047##
##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052##
##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057##
##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062##
##STR00063## ##STR00064## ##STR00065## ##STR00066## ##STR00067##
##STR00068## ##STR00069## ##STR00070## ##STR00071## ##STR00072##
##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077##
##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082##
##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087##
##STR00088## ##STR00089## ##STR00090##
A first device comprising an organic light emitting device is also
provided. The device further comprises an anode, a cathode, and an
organic layer, disposed between the anode and the cathode. The
organic layer comprises a compound having Formula I, as described
above.
R.sub.1, R.sub.2, R.sub.3, and R.sub.4 may represent mono, di, tri,
or tetra substitutions. R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are
independently selected from the group consisting of hydrogen,
alkyl, alkoxy, amino, alkenyl, alkynyl, aryl and heteroaryl.
Ar.sub.1, Ar.sub.2, and Ar.sub.3 are independently selected from
aryl or heteroaryl. Ar.sub.1, Ar.sub.2, and Ar.sub.3 may be further
substituted. X is C or N.
In one aspect, Ar.sub.1, Ar.sub.2, and Ar.sub.3 are independently
selected from the group consisting of phenyl, pyridine,
naphthalene, biphenyl, terphenyl, fluorene, dibenzofuran,
dibenzothiophene, phenanthrene, and triphenylene. Ar.sub.1,
Ar.sub.2, and Ar.sub.3 are independently further substituted with a
substituent selected from the group consisting of hydrogen, alkyl,
alkoxy, amino, alkenyl, alkynyl, aryl and heteroaryl, but the
substituent is not an aryl or heteroaryl fused directly to
Ar.sub.1, Ar.sub.2, and Ar.sub.3. Preferably, Ar.sub.1 and Ar.sub.2
are independently selected from the group consisting of phenyl,
pyridine, and naphthalene. Preferably, Ar.sub.3 is selected from
the group consisting of phenyl, biphenyl, dibenzofuran, and
dibenzothiophene.
In another aspect, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are
hydrogen.
Specific examples of devices containing compounds comprising
bicarbazole are also provided. In particular, the compound is
selected from the group consisting of Compound 1-Compound 184.
In one aspect, the organic layer is deposited using solution
processing.
In one aspect, the organic layer is an emissive layer and the
compound having Formula I is a host.
In another aspect, the organic layer further comprises an emissive
dopant having the formula:
##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095##
##STR00096## ##STR00097## ##STR00098## ##STR00099##
##STR00100##
In one aspect, the first device is a consumer product. In another
aspect, the first device is an organic light emitting device.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows an organic light emitting device.
FIG. 2 shows an inverted organic light emitting device that does
not have a separate electron transport layer.
FIG. 3 shows a bicarbazole compound with a nitrogen-containing
heterocycle substitution at the 9-position.
DETAILED DESCRIPTION
Generally, an OLED comprises at least one organic layer disposed
between and electrically connected to an anode and a cathode. When
a current is applied, the anode injects holes and the cathode
injects electrons into the organic layer(s). The injected holes and
electrons each migrate toward the oppositely charged electrode.
When an electron and hole localize on the same molecule, an
"exciton," which is a localized electron-hole pair having an
excited energy state, is formed. Light is emitted when the exciton
relaxes via a photoemissive mechanism. In some cases, the exciton
may be localized on an excimer or an exciplex. Non-radiative
mechanisms, such as thermal relaxation, may also occur, but are
generally considered undesirable.
The initial OLEDs used emissive molecules that emitted light from
their singlet states ("fluorescence") as disclosed, for example, in
U.S. Pat. No. 4,769,292, which is incorporated by reference in its
entirety. Fluorescent emission generally occurs in a time frame of
less than 10 nanoseconds.
More recently, OLEDs having emissive materials that emit light from
triplet states ("phosphorescence") have been demonstrated. Baldo et
al., "Highly Efficient Phosphorescent Emission from Organic
Electroluminescent Devices," Nature, vol. 395, 151-154, 1998;
("Baldo-I") and Baldo et al., "Very high-efficiency green organic
light-emitting devices based on electrophosphorescence," Appl.
Phys. Lett., vol. 75, No. 3, 4-6 (1999) ("Baldo-II"), which are
incorporated by reference in their entireties. Phosphorescence is
described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6,
which are incorporated by reference.
FIG. 1 shows an organic light emitting device 100. The figures are
not necessarily drawn to scale. Device 100 may include a substrate
110, an anode 115, a hole injection layer 120, a hole transport
layer 125, an electron blocking layer 130, an emissive layer 135, a
hole blocking layer 140, an electron transport layer 145, an
electron injection layer 150, a protective layer 155, and a cathode
160. Cathode 160 is a compound cathode having a first conductive
layer 162 and a second conductive layer 164. Device 100 may be
fabricated by depositing the layers described, in order. The
properties and functions of these various layers, as well as
example materials, are described in more detail in U.S. Pat. No.
7,279,704 at cols. 6-10, which are incorporated by reference.
More examples for each of these layers are available. For example,
a flexible and transparent substrate-anode combination is disclosed
in U.S. Pat. No. 5,844,363, which is incorporated by reference in
its entirety. An example of a p-doped hole transport layer is
m-MTDATA doped with F.sub.4-TCNQ at a molar ratio of 50:1, as
disclosed in U.S. Patent Application Publication No. 2003/0230980,
which is incorporated by reference in its entirety. Examples of
emissive and host materials are disclosed in U.S. Pat. No.
6,303,238 to Thompson et al., which is incorporated by reference in
its entirety. An example of an n-doped electron transport layer is
BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S.
Patent Application Publication No. 2003/0230980, which is
incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436
and 5,707,745, which are incorporated by reference in their
entireties, disclose examples of cathodes including compound
cathodes having a thin layer of metal such as Mg:Ag with an
overlying transparent, electrically-conductive, sputter-deposited
ITO layer. The theory and use of blocking layers is described in
more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application
Publication No. 2003/0230980, which are incorporated by reference
in their entireties. Examples of injection layers are provided in
U.S. Patent Application Publication No. 2004/0174116, which is
incorporated by reference in its entirety. A description of
protective layers may be found in U.S. Patent Application
Publication No. 2004/0174116, which is incorporated by reference in
its entirety.
FIG. 2 shows an inverted OLED 200. The device includes a substrate
210, a cathode 215, an emissive layer 220, a hole transport layer
225, and an anode 230. Device 200 may be fabricated by depositing
the layers described, in order. Because the most common OLED
configuration has a cathode disposed over the anode, and device 200
has cathode 215 disposed under anode 230, device 200 may be
referred to as an "inverted" OLED. Materials similar to those
described with respect to device 100 may be used in the
corresponding layers of device 200. FIG. 2 provides one example of
how some layers may be omitted from the structure of device
100.
The simple layered structure illustrated in FIGS. 1 and 2 is
provided by way of non-limiting example, and it is understood that
embodiments of the invention may be used in connection with a wide
variety of other structures. The specific materials and structures
described are exemplary in nature, and other materials and
structures may be used. Functional OLEDs may be achieved by
combining the various layers described in different ways, or layers
may be omitted entirely, based on design, performance, and cost
factors. Other layers not specifically described may also be
included. Materials other than those specifically described may be
used. Although many of the examples provided herein describe
various layers as comprising a single material, it is understood
that combinations of materials, such as a mixture of host and
dopant, or more generally a mixture, may be used. Also, the layers
may have various sublayers. The names given to the various layers
herein are not intended to be strictly limiting. For example, in
device 200, hole transport layer 225 transports holes and injects
holes into emissive layer 220, and may be described as a hole
transport layer or a hole injection layer. In one embodiment, an
OLED may be described as having an "organic layer" disposed between
a cathode and an anode. This organic layer may comprise a single
layer, or may further comprise multiple layers of different organic
materials as described, for example, with respect to FIGS. 1 and
2.
Structures and materials not specifically described may also be
used, such as OLEDs comprised of polymeric materials (PLEDs) such
as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is
incorporated by reference in its entirety. By way of further
example, OLEDs having a single organic layer may be used. OLEDs may
be stacked, for example as described in U.S. Pat. No. 5,707,745 to
Forrest et al, which is incorporated by reference in its entirety.
The OLED structure may deviate from the simple layered structure
illustrated in FIGS. 1 and 2. For example, the substrate may
include an angled reflective surface to improve out-coupling, such
as a mesa structure as described in U.S. Pat. No. 6,091,195 to
Forrest et al., and/or a pit structure as described in U.S. Pat.
No. 5,834,893 to Bulovic et al., which are incorporated by
reference in their entireties.
Unless otherwise specified, any of the layers of the various
embodiments may be deposited by any suitable method. For the
organic layers, preferred methods include thermal evaporation,
ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and
6,087,196, which are incorporated by reference in their entireties,
organic vapor phase deposition (OVPD), such as described in U.S.
Pat. No. 6,337,102 to Forrest et al., which is incorporated by
reference in its entirety, and deposition by organic vapor jet
printing (OVJP), such as described in U.S. patent application Ser.
No. 10/233,470, which is incorporated by reference in its entirety.
Other suitable deposition methods include spin coating and other
solution based processes. Solution based processes are preferably
carried out in nitrogen or an inert atmosphere. For the other
layers, preferred methods include thermal evaporation. Preferred
patterning methods include deposition through a mask, cold welding
such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which
are incorporated by reference in their entireties, and patterning
associated with some of the deposition methods such as ink jet and
OVJD. Other methods may also be used. The materials to be deposited
may be modified to make them compatible with a particular
deposition method. For example, substituents such as alkyl and aryl
groups, branched or unbranched, and preferably containing at least
3 carbons, may be used in small molecules to enhance their ability
to undergo solution processing. Substituents having 20 carbons or
more may be used, and 3-20 carbons is a preferred range. Materials
with asymmetric structures may have better solution processibility
than those having symmetric structures, because asymmetric
materials may have a lower tendency to recrystallize. Dendrimer
substituents may be used to enhance the ability of small molecules
to undergo solution processing.
Devices fabricated in accordance with embodiments of the invention
may be incorporated into a wide variety of consumer products,
including flat panel displays, computer monitors, televisions,
billboards, lights for interior or exterior illumination and/or
signaling, heads up displays, fully transparent displays, flexible
displays, laser printers, telephones, cell phones, personal digital
assistants (PDAs), laptop computers, digital cameras, camcorders,
viewfinders, micro-displays, vehicles, a large area wall, theater
or stadium screen, or a sign. Various control mechanisms may be
used to control devices fabricated in accordance with the present
invention, including passive matrix and active matrix. Many of the
devices are intended for use in a temperature range comfortable to
humans, such as 18 degrees C. to 30 degrees C., and more preferably
at room temperature (20-25 degrees C.).
The materials and structures described herein may have applications
in devices other than OLEDs. For example, other optoelectronic
devices such as organic solar cells and organic photodetectors may
employ the materials and structures. More generally, organic
devices, such as organic transistors, may employ the materials and
structures.
The terms halo, halogen, alkyl, cycloalkyl, alkenyl, alkynyl,
arylkyl, heterocyclic group, aryl, aromatic group, and heteroaryl
are known to the art, and are defined in U.S. Pat. No. 7,279,704 at
cols. 31-32, which are incorporated herein by reference.
Novel bicarbazole containing compounds are provided (illustrated in
FIG. 3). More specifically, these compounds contain a
3,3'-bicarbazole core and triazine or pyrimidine substitution at
the 9-position. These compounds may be used as hosts for
phosphorescent OLEDs.
Carbazole containing compounds for use as OLED materials have been
previously described. In particular, 3,3'-bicarbazole compounds
have good hole transporting properties, but have poor stability
toward electrons. Alkyl and aryl substituted 3,3'-bicarbazole
compounds have been used as hole transporting materials and hosts
in OLEDs; however, these compounds also have imbalanced charge
transporting properties and poor electron stability and may provide
devices with low efficiency and limited lifetime. For example, a
diaryl substituted 3,3'-bicarbazole, i.e. H1, has a HOMO around 5.6
eV, very good for hole transporting but poor for electron
transporting and stability. Therefore, the 3,3'-bicarbazole
compounds reported in the literature may have limited use.
In the present invention, nitrogen containing electron deficient
heterocycles were introduced to 3,3'-bicarbazole compounds. In
particular, the compounds contain a 3,3'-bicarbazole core and
triazine or pyrimidine substitution at the 9 position. The nitrogen
containing heterocycle tunes the HOMO/LUMO levels as well as
increases the compound's stability toward electrons. In addition,
these compounds contain a donor part, i.e. bicarbazole, and an
acceptor part, i.e. electron deficient nitrogen heterocycle.
Without being bound by theory, it is believed that these
donor-acceptor type molecules can shrink singlet and triplet gap
and improve stability to both hole and electrons. Therefore, these
3,3'-bicarbazole compounds containing a nitrogen heterocycle may
provide devices having better stability and lower operating
voltage.
Compounds comprising a bicarbazole are provided. The compounds have
the formula:
##STR00101##
R.sub.1, R.sub.2, R.sub.3, and R.sub.4 may represent mono, di, tri,
or tetra substitutions. R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are
independently selected from the group consisting of hydrogen,
alkyl, alkoxy, amino, alkenyl, alkynyl, aryl and heteroaryl.
Ar.sub.1, Ar.sub.2, and Ar.sub.3 are independently selected from
aryl or heteroaryl. Ar.sub.1, Ar.sub.2, and Ar.sub.3 may be further
substituted. X is C or N.
In one aspect, Ar.sub.1, Ar.sub.2, and Ar.sub.3 are independently
selected from the group consisting of phenyl, pyridine,
naphthalene, biphenyl, terphenyl, fluorene, dibenzofuran,
dibenzothiophene, phenanthrene, and triphenylene, and Ar.sub.1,
Ar.sub.2, and Ar.sub.3 are independently further substituted with a
substituent selected from the group consisting of hydrogen, alkyl,
alkoxy, amino, alkenyl, alkynyl, aryl and heteroaryl, but the
substituent is not an aryl or heteroaryl fused directly to
Ar.sub.1, Ar.sub.2, and Ar.sub.3. Preferably, Ar.sub.1 and Ar.sub.2
are independently selected from the group consisting of phenyl,
pyridine, and naphthalene. Preferably, Ar.sub.3 is selected from
the group consisting of phenyl, biphenyl, dibenzofuran, and
dibenzothiophene.
In another aspect, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are
hydrogen.
Specific examples of compounds comprising bicarbazole are also
provided. In particular, the compound is selected from the group
consisting of:
##STR00102## ##STR00103## ##STR00104## ##STR00105## ##STR00106##
##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111##
##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116##
##STR00117## ##STR00118## ##STR00119## ##STR00120## ##STR00121##
##STR00122## ##STR00123## ##STR00124## ##STR00125## ##STR00126##
##STR00127## ##STR00128## ##STR00129## ##STR00130## ##STR00131##
##STR00132## ##STR00133## ##STR00134## ##STR00135## ##STR00136##
##STR00137## ##STR00138## ##STR00139## ##STR00140## ##STR00141##
##STR00142## ##STR00143## ##STR00144## ##STR00145## ##STR00146##
##STR00147## ##STR00148## ##STR00149## ##STR00150## ##STR00151##
##STR00152## ##STR00153## ##STR00154## ##STR00155## ##STR00156##
##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161##
##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166##
##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171##
##STR00172## ##STR00173## ##STR00174## ##STR00175## ##STR00176##
##STR00177## ##STR00178## ##STR00179## ##STR00180## ##STR00181##
##STR00182## ##STR00183## ##STR00184## ##STR00185## ##STR00186##
##STR00187## ##STR00188## ##STR00189## ##STR00190## ##STR00191##
##STR00192## ##STR00193##
A first device comprising an organic light emitting device is also
provided. The device further comprises an anode, a cathode, and an
organic layer, disposed between the anode and the cathode. The
organic layer comprises a compound having Formula I, as described
above.
R.sub.1, R.sub.2, R.sub.3, and R.sub.4 may represent mono, di, tri,
or tetra substitutions. R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are
independently selected from the group consisting of hydrogen,
alkyl, alkoxy, amino, alkenyl, alkynyl, aryl and heteroaryl.
Ar.sub.1, Ar.sub.2, and Ar.sub.3 are independently selected from
aryl or heteroaryl. Ar.sub.1, Ar.sub.2, and Ar.sub.3 may be further
substituted. X is C or N.
In one aspect, Ar.sub.1, Ar.sub.2, and Ar.sub.3 are independently
selected from the group consisting of phenyl, pyridine,
naphthalene, biphenyl, terphenyl, fluorene, dibenzofuran,
dibenzothiophene, phenanthrene, and triphenylene. Ar.sub.1,
Ar.sub.2, and Ar.sub.3 are independently further substituted with a
substituent selected from the group consisting of hydrogen, alkyl,
alkoxy, amino, alkenyl, alkynyl, aryl and heteroaryl, but the
substituent is not an aryl or heteroaryl fused directly to
Ar.sub.1, Ar.sub.2, and Ar.sub.3. Preferably, Ar.sub.1 and Ar.sub.2
are independently selected from the group consisting of phenyl,
pyridine, and naphthalene. Preferably, Ar.sub.3 is selected from
the group consisting of phenyl, biphenyl, dibenzofuran, and
dibenzothiophene.
In another aspect, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are
hydrogen.
Specific examples of devices containing compounds comprising
bicarbazole are also provided. In particular, the compound is
selected from the group consisting of Compound 1-Compound 184.
In one aspect, the organic layer is deposited using solution
processing.
In one aspect, the organic layer is an emissive layer and the
compound having Formula I is a host.
In another aspect, the organic layer further comprises an emissive
dopant having the formula:
##STR00194## ##STR00195## ##STR00196## ##STR00197## ##STR00198##
##STR00199## ##STR00200## ##STR00201## ##STR00202##
##STR00203##
In one aspect, the first device is a consumer product. In another
aspect, the first device is an organic light emitting device.
Combination with Other Materials
The materials described herein as useful for a particular layer in
an organic light emitting device may be used in combination with a
wide variety of other materials present in the device. For example,
emissive dopants disclosed herein may be used in conjunction with a
wide variety of hosts, transport layers, blocking layers, injection
layers, electrodes and other layers that may be present. The
materials described or referred to below are non-limiting examples
of materials that may be useful in combination with the compounds
disclosed herein, and one of skill in the art can readily consult
the literature to identify other materials that may be useful in
combination.
HIL/HTL:
A hole injecting/transporting material to be used in the present
invention is not particularly limited, and any compound may be used
as long as the compound is typically used as a hole
injecting/transporting material. Examples of the material include,
but not limit to: a phthalocyanine or porphryin derivative; an
aromatic amine derivative; an indolocarbazole derivative; a polymer
containing fluorohydrocarbon; a polymer with conductivity dopants;
a conducting polymer, such as PEDOT/PSS; a self-assembly monomer
derived from compounds such as phosphonic acid and sliane
derivatives; a metal oxide derivative, such as MoO.sub.x; a p-type
semiconducting organic compound, such as
1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex,
and a cross-linkable compounds.
Examples of aromatic amine derivatives used in HIL or HTL include,
but not limit to the following general structures:
##STR00204##
Each of Ar.sup.1 to Ar.sup.9 is selected from the group consisting
aromatic hydrocarbon cyclic compounds such as benzene, biphenyl,
triphenyl, triphenylene, naphthalene, anthracene, phenalene,
phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group
consisting aromatic heterocyclic compounds such as
dibenzothiophene, dibenzofuran, dibenzoselenophene, furan,
thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole,
indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole,
imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole,
dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine,
triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole,
indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole,
quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline,
naphthyridine, phthalazine, pteridine, xanthene, acridine,
phenazine, phenothiazine, phenoxazine, benzofuropyridine,
furodipyridine, benzothienopyridine, thienodipyridine,
benzoselenophenopyridine, and selenophenodipyridine; and group
consisting 2 to 10 cyclic structural units which are groups of the
same type or different types selected from the aromatic hydrocarbon
cyclic group and the aromatic heterocyclic group and are bonded to
each other directly or via at least one of oxygen atom, nitrogen
atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain
structural unit and the aliphatic cyclic group. Wherein each Ar is
further substituted by a substituent selected from the group
consisting of hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl,
arylalkyl, heteroalkyl, aryl and heteroaryl.
In one aspect, Ar.sup.1 to Ar.sup.9 is independently selected from
the group consisting of:
##STR00205##
k is an integer from 1 to 20; X.sup.1 to X.sup.8 is CH or N;
Ar.sup.1 has the same group defined above.
Examples of metal complexes used in HIL or HTL include, but not
limit to the following general formula:
##STR00206##
M is a metal, having an atomic weight greater than 40;
(Y.sup.1-Y.sup.2) is a bidentate ligand, Y1 and Y.sup.2 are
independently selected from C, N, O, P, and S; L is an ancillary
ligand; m is an integer value from 1 to the maximum number of
ligands that may be attached to the metal; and m+n is the maximum
number of ligands that may be attached to the metal.
In one aspect, (Y.sup.1-Y.sup.2) is a 2-phenylpyridine
derivative.
In another aspect, (Y.sup.1-Y.sup.2) is a carbene ligand.
In another aspect, M is selected from Ir, Pt, Os, and Zn.
In a further aspect, the metal complex has a smallest oxidation
potential in solution vs. Fc.sup.+/Fc couple less than about 0.6
V.
Host:
The light emitting layer of the organic EL device of the present
invention preferably contains at least a metal complex as light
emitting material, and may contain a host material using the metal
complex as a dopant material. Examples of the host material are not
particularly limited, and any metal complexes or organic compounds
may be used as long as the triplet energy of the host is larger
than that of the dopant.
Examples of metal complexes used as host are preferred to have the
following general formula:
##STR00207##
M is a metal; (Y.sup.3-Y.sup.4) is a bidentate ligand, Y.sup.3 and
Y.sup.4 are independently selected from C, N, O, P, and S; L is an
ancillary ligand; m is an integer value from 1 to the maximum
number of ligands that may be attached to the metal; and m+n is the
maximum number of ligands that may be attached to the metal.
In one aspect, the metal complexes are:
##STR00208##
(O--N) is a bidentate ligand, having metal coordinated to atoms O
and N.
In another aspect, M is selected from Ir and Pt.
In a further aspect, (Y.sup.3-Y.sup.4) is a carbene ligand.
Examples of organic compounds used as host are selected from the
group consisting aromatic hydrocarbon cyclic compounds such as
benzene, biphenyl, triphenyl, triphenylene, naphthalene,
anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene,
perylene, azulene; group consisting aromatic heterocyclic compounds
such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan,
thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole,
indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole,
imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole,
dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine,
triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole,
indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole,
quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline,
naphthyridine, phthalazine, pteridine, xanthene, acridine,
phenazine, phenothiazine, phenoxazine, benzofuropyridine,
furodipyridine, benzothienopyridine, thienodipyridine,
benzoselenophenopyridine, and selenophenodipyridine; and group
consisting 2 to 10 cyclic structural units which are groups of the
same type or different types selected from the aromatic hydrocarbon
cyclic group and the aromatic heterocyclic group and are bonded to
each other directly or via at least one of oxygen atom, nitrogen
atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain
structural unit and the aliphatic cyclic group. Wherein each group
is further substituted by a substituent selected from the group
consisting of hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl,
arylalkyl, heteroalkyl, aryl and heteroaryl.
In one aspect, host compound contains at least one of the following
groups in the molecule:
##STR00209## ##STR00210##
R.sup.1 to R.sup.7 is independently selected from the group
consisting of hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl,
arylalkyl, heteroalkyl, aryl and heteroaryl, when it is aryl or
heteroaryl, it has the similar definition as Ar's mentioned
above.
k is an integer from 0 to 20.
X.sup.1 to X.sup.8 is selected from CH or N.
HBL:
A hole blocking layer (HBL) may be used to reduce the number of
holes and/or excitons that leave the emissive layer. The presence
of such a blocking layer in a device may result in substantially
higher efficiencies as compared to a similar device lacking a
blocking layer. Also, a blocking layer may be used to confine
emission to a desired region of an OLED.
In one aspect, compound used in HBL contains the same molecule used
as host described above.
In another aspect, compound used in HBL contains at least one of
the following groups in the molecule:
##STR00211##
k is an integer from 0 to 20; L is an ancillary ligand, m is an
integer from 1 to 3.
ETL:
Electron transport layer (ETL) may include a material capable of
transporting electrons. Electron transport layer may be intrinsic
(undoped), or doped. Doping may be used to enhance conductivity.
Examples of the ETL material are not particularly limited, and any
metal complexes or organic compounds may be used as long as they
are typically used to transport electrons.
In one aspect, compound used in ETL contains at least one of the
following groups in the molecule:
##STR00212##
R.sup.1 is selected from the group consisting of hydrogen, alkyl,
alkoxy, amino, alkenyl, alkynyl, arylalkyl, heteroalkyl, aryl and
heteroaryl, when it is aryl or heteroaryl, it has the similar
definition as Ar's mentioned above.
Ar.sup.1 to Ar.sup.3 has the similar definition as Ar's mentioned
above.
k is an integer from 0 to 20.
X.sup.1 to X.sup.8 is selected from CH or N.
In another aspect, the metal complexes used in ETL contains, but
not limit to the following general formula:
##STR00213##
(O--N) or (N--N) is a bidentate ligand, having metal coordinated to
atoms O, N or N, N; L is an ancillary ligand; m is an integer value
from 1 to the maximum number of ligands that may be attached to the
metal.
In any above-mentioned compounds used in each layer of OLED device,
the hydrogen atoms attached to conjugated rings can be partially or
fully deuterated.
The materials described herein as useful for a particular layer in
an organic light emitting device may be used in combination with a
wide variety of other materials present in the device. For example,
emissive dopants disclosed herein may be used in conjunction with a
wide variety of hosts, transport layers, blocking layers, injection
layers, electrodes and other layers that may be present. The
materials described or referred to below are non-limiting examples
of materials that may be useful in combination with the compounds
disclosed herein, and one of skill in the art can readily consult
the literature to identify other materials that may be useful in
combination.
In addition to and/or in combination with the materials disclosed
herein, many hole injection materials, hole transporting materials,
host materials, dopant materials, exiton/hole blocking layer
materials, electron transporting and electron injecting materials
may be used in an OLED. Non-limiting examples of the materials that
may be used in an OLED in combination with materials disclosed
herein are listed in Table 1 below. Table 1 lists non-limiting
classes of materials, non-limiting examples of compounds for each
class, and references that disclose the materials.
TABLE-US-00001 TABLE 1 MATERIAL EXAMPLES OF MATERIAL PUBLICATIONS
Hole injection materials Phthalocyanine and porphryin compounds
##STR00214## Appl. Phys. Lett. 69, 2160 (1996) Starburst
triarylamines ##STR00215## J. Lumin. 72-74, 985 (1997) CF.sub.x
Fluorohydrocarbon polymer ##STR00216## Appl. Phys. Lett. 78, 673
(2001) Conducting polymers (e.g., PEDOT:PSS, polyaniline,
polypthiophene) ##STR00217## Synth. Met. 87, 171 (1997)
WO2007002683 Phosphonic acid and sliane SAMs ##STR00218##
US20030162053 Triarylamine or polythiophene polymers with
conductivity dopants ##STR00219## EA01725079A1 and ##STR00220##
##STR00221## Arylamines complexed with metal oxides such as
molybdenum and tungsten oxides ##STR00222## SID Symposium Digest,
37, 923 (2006) WO2009018009 p-type semiconducting organic complexes
##STR00223## US20020158242 Metal organometallic complexes
##STR00224## US20060240279 Cross-linkable compounds ##STR00225##
US20080220265 Hole transporting materials Triarylamines (e.g., TPD,
.alpha.-NPD) ##STR00226## Appl. Phys. Lett. 51, 913 (1987)
##STR00227## U.S. Pat. No. 5,061,569 ##STR00228## EP650955
##STR00229## J. Mater. Chem. 3, 319 (1993) ##STR00230## Appl. Phys.
Lett. 90, 183503 (2007) ##STR00231## Appl. Phys. Lett. 90, 183503
(2007) Triaylamine on spirofluorene core ##STR00232## Synth. Met.
91, 209 (1997) Arylamine carbazole compounds ##STR00233## Adv.
Mater. 6, 677 (1994), US20080124572 Triarylamine with
(di)benzothiophene/ (di)benzofuran ##STR00234## US20070278938,
US20080106190 Indolocarbazoles ##STR00235## Synth. Met. 111, 421
(2000) Isoindole compounds ##STR00236## Chem. Mater. 15, 3148
(2003) Metal carbene complexes ##STR00237## US20080018221
Phosphorescent OLED host materials Red hosts Arylcarbazoles
##STR00238## Appl. Phys. Lett. 78, 1622 (2001) Metal
8-hydroxyquinolates (e.g., Alq.sub.3, BAlq) ##STR00239## Nature
395, 151 (1998) ##STR00240## US20060202194 ##STR00241##
WO2005014551 ##STR00242## WO2006072002 Metal phenoxybenzothiazole
compounds ##STR00243## Appl. Phys. Lett. 90, 123509 (2007)
Conjugated oligomers and polymers (e.g., polyfluorene) ##STR00244##
Org. Electron. 1, 15 (2000) Aromatic fused rings ##STR00245##
WO2009066779, WO2009066778, WO2009063833, US20090045730,
US20090045731, WO2009008311, US20090008605, US20090009065 Zinc
complexes ##STR00246## WO2009062578 Green hosts Arylcarbazoles
##STR00247## Appl. Phys. Lett. 78, 1622 (2001) ##STR00248##
US20030175553 ##STR00249## WO2001039234 Aryltriphenylene compounds
##STR00250## US20060280965 ##STR00251## US20060280965 ##STR00252##
WO2009021126 Donor acceptor type molecules ##STR00253##
WO2008056746 Aza-carbazole/ DBT/DBF ##STR00254## JP2008074939
Polymers (e.g., PVK) ##STR00255## Appl. Phys. Lett. 77, 2280 (2000)
Spirofluorene compounds ##STR00256## WO2004093207 Metal
phenoxybenzooxazole compounds ##STR00257## WO2005089025
##STR00258## WO2006132173 ##STR00259## JP200511610
Spirofluorene-carbazole compounds ##STR00260## JP2007254297
##STR00261## JP2007254297 Indolocabazoles ##STR00262## WO2007063796
##STR00263## WO2007063754 5-member ring electron deficient
heterocycles (e.g., triazole, oxadiazole) ##STR00264## J. Appl.
Phys. 90, 5048 (2001) ##STR00265## WO2004107822 Tetraphenylene
complexes ##STR00266## US20050112407 Metal phenoxypyridine
compounds ##STR00267## WO2005030900 Metal coordination complexes
(e.g., Zn, Al with N.DELTA.N ligands) ##STR00268## US20040137268,
US20040137267 Blue hosts Arylcarbazoles ##STR00269## Appl. Phys.
Lett, 82, 2422 (2003) ##STR00270## US20070190359 Dibenzothiophene/
Dibenzofuran-carbazole compounds ##STR00271## WO2006114966,
US20090167162 ##STR00272## US20090167162 ##STR00273## WO2009086028
##STR00274## US20090030202, US20090017330 Silicon aryl compounds
##STR00275## US20050238919 ##STR00276## WO2009003898
Silicon/Germanium aryl compounds ##STR00277## EP2034538A Aryl
benzoyl ester ##STR00278## WO2006100298 High triplet metal
organometallic complex ##STR00279## U.S. Pat. No. 7,154,114
Phosphorescent dopants Red dopants Heavy metal porphyrins (e.g.,
PtOEP) ##STR00280## Nature 395, 151 (1998) Iridium(III)
organometallic complexes ##STR00281## Appl. Phys. Lett. 78, 1622
(2001) ##STR00282## US2006835469 ##STR00283## US2006835469
##STR00284## US20060202194 ##STR00285## US20060202194 ##STR00286##
US20070087321 ##STR00287## US20070087321 ##STR00288## Adv. Mater.
19, 739 (2007) ##STR00289## WO2009100991 ##STR00290## WO2008101842
Platinum(II) organometallic complexes ##STR00291## WO2003040257
Osminum(III) complexes ##STR00292## Chem. Mater. 17, 3532 (2005)
Ruthenium(II) complexes ##STR00293## Adv. Mater. 17, 1059 (2005)
Rhenium (I), (II), and (III) complexes ##STR00294## US20050244673
Green dopants Iridium(III) organometallic complexes ##STR00295##
Inorg. Chem. 40, 1704 (2001) ##STR00296## US20020034656
##STR00297## U.S. Pat. No. 7,332,232 ##STR00298## US20090108737
##STR00299## US20090039776 ##STR00300## U.S. Pat. No. 6,921,915
##STR00301## U.S. Pat. No. 6,687,266 ##STR00302## Chem. Mater. 16,
2480 (2004) ##STR00303## US20070190359 ##STR00304## US20060008670
JP2007123392 ##STR00305## Adv. Mater. 16, 2003 (2004) ##STR00306##
Angew. Chem. Int. Ed. 2006, 45, 7800 ##STR00307## WO2009050290
##STR00308## US20090165846 ##STR00309## US20080015355 Monomer for
polymeric metal organometallic compounds ##STR00310## U.S. Pat. No.
7,250,226, U.S. Pat. No. 7,396,598 Pt(II) organometallic complexes,
including polydentated ligands ##STR00311## Appl. Phys. Lett. 86,
153505 (2005) ##STR00312## Appl. Phys. Lett. 86, 153505 (2005)
##STR00313## Chem. Lett. 34, 592 (2005) ##STR00314## WO2002015645
##STR00315## US20060263635 Cu complexes ##STR00316## WO2009000673
Gold complexes ##STR00317## Chem. Commun. 2906 (2005) Rhenium(III)
complexes ##STR00318## Inorg. Chem. 42, 1248 (2003) Deuterated
organometallic complexes ##STR00319## US20030138657
Organometallic complexes with two or more metal centers
##STR00320## US20030152802 ##STR00321## U.S. Pat. No. 7,090,928
Blue dopants Iridium(III) organometallic complexes ##STR00322##
WO2002002714 ##STR00323## WO2006009024 ##STR00324## US20060251923
##STR00325## U.S. Pat. No. 7,393,599, WO2006056418, US20050260441,
WO2005019373 ##STR00326## U.S. Pat. No. 7,534,505 ##STR00327## U.S.
Pat. No. 7,445,855 ##STR00328## US20070190359, US20080297033
##STR00329## U.S. Pat. No. 7,338,722 ##STR00330## US20020134984
##STR00331## Angew. Chem. Int. Ed. 47, 1 (2008) ##STR00332## Chem.
Mater. 18, 5119 (2006) ##STR00333## Inorg. Chem. 46, 4308 (2007)
##STR00334## WO2005123873 ##STR00335## WO2005123873 ##STR00336##
WO2007004380 ##STR00337## WO2006082742 Osmium(II) complexes
##STR00338## U.S. Pat. No. 7,279,704 ##STR00339## Organometallics
23, 3745 (2004) Gold complexes ##STR00340## Appl. Phys. Lett. 74,
1361 (1999) Platinum(II) complexes ##STR00341## WO2006098120,
WO2006103874 Exciton/hole blocking layer materials Bathocuprine
compounds (e.g., BCP, BPhen) ##STR00342## Appl. Phys. Lett. 75, 4
(1999) ##STR00343## Appl. Phys. Lett. 79, 449 (2001) Metal
8-hydroxyquinolates (e.g., BAlq) ##STR00344## Appl. Phys. Lett. 81,
162 (2002) 5-member ring electron deficient heterocycles such as
triazole, oxadiazole, imidazole, benzoimidazole ##STR00345## Appl.
Phys. Lett. 81, 162 (2002) Triphenylene compounds ##STR00346##
US20050025993 Fluorinated aromatic compounds ##STR00347## Appl.
Phys. Lett. 79, 156 (2001) Phenothiazine-S-oxide ##STR00348##
WO2008132085 Electron transporting materials Anthracene-
benzoimidazole compounds ##STR00349## WO2003060956 ##STR00350##
US20090179554 Aza triphenylene derivatives ##STR00351##
US20090115316 Anthracene- benzothiazole compounds ##STR00352##
Appl. Phys. Lett. 89, 063504 (2006) Metal 8-hydroxyquinolates
(e.g., Alq.sub.3, Zrq.sub.4) ##STR00353## Appl. Phys. Lett. 51, 913
(1987) U.S. Pat. No. 7,230,107 Metal hydroxybenoquinolates
##STR00354## Chem. Lett. 5, 905 (1993) Bathocuprine compounds such
as BCP, BPhen, etc ##STR00355## Appl. Phys. Lett. 91, 263503 (2007)
##STR00356## Appl. Phys. Lett. 79, 449 (2001) 5-member ring
electron deficient heterocycles (e.g., triazole, oxadiazole,
imidazole, benzoimidazole) ##STR00357## Appl. Phys. Lett. 74, 865
(1999) ##STR00358## Appl. Phys. Lett. 55, 1489 (1989) ##STR00359##
Jpn. J. Apply. Phys. 32, L917 (1993) Silole compounds ##STR00360##
Org. Electron. 4, 113 (2003) Arylborane compounds ##STR00361## J.
Am. Chem. Soc. 120, 9714 (1998) Fluorinated aromatic compounds
##STR00362## J. Am. Chem. Soc. 122, 1832 (2000) Fullerene (e.g.,
C60) ##STR00363## US20090101870 Triazine complexes ##STR00364##
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6,528,187
EXPERIMENTAL
Compound Examples
Example 1. Synthesis of Compound 1
##STR00366##
Synthesis of 3-iodo-9H-carbazole
To a solution of 9H-carbazole (5.57 g, 33.3 mmol) and KI (3.68 g,
22.2 mmol) in AcOH (92 mL) was heated to 100.degree. C. for 1 h.
KIO.sub.3 (3.57 g, 16.7 mmol) was added in portions to the
solution, and the resulting mixture was stirred for another 2 h at
100.degree. C. The mixture was poured into water (500 mL) and the
precipitation was collected by filtration and washed with hot
water. Recrystallization was made in DCM to afford 6.8 g (70%) of
product as a white solid.
##STR00367##
Synthesis of
9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole
To a solution of 3-bromo-9-phenyl-9H-carbazole (20.3 g, 63 mmol) in
THF (150 mL) at -78.degree. C. was added 47.25 mL (75.8 mmol) of
n-butyllithium (1.6 M in hexane). The mixture was stirred at
-78.degree. C. for 1 h. 21 mL (100 mmol) of
2-isopropoxy-4,4,5,5-tetramethyl-[1,3,2]-dioxaborolane was added to
the solution, and the resulting mixture was warmed to room
temperature and stirred for 8 h. The mixture was poured into water
and extracted with dichloromethane. The organic extracts were
washed with brine and dried over magnesium sulfate. The solvent was
removed by rotary evaporation, and recrystallization was made in
hexane to afford 19.3 g (83%) of product as a white solid.
##STR00368##
Synthesis of 3-(9-phenyl-9H-carbazol-3-yl)-9H-carbazole
To a solution of 3-iodo-9H-carbazole (879 mg, 3.0 mmol),
Pd(PPh.sub.3).sub.4 (165 mg, 0.15 mmol),
9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole
(1.29 g, 4.5 mmol) and K.sub.3PO.sub.4 (1.8 g, 18.0 mmol) in
dioxane (5 mL). The solution was heated to 85.degree. C. with
vigorous stirring for 48 h under argon atmosphere. The mixture was
poured into water and extracted with DCM. The organic extracts were
washed with brine and dried over MgSO.sub.4. The solvent was
removed by rotary evaporation, and recrystallization was made in
DCM to afford 900 mg (74%) of product.
##STR00369##
Synthesis of
9-(4,6-diphenyl-1,3,5-triazin-2-yl)-3-(9-phenyl-9H-carbazol-3-yl)-9H-carb-
azole (Compound 1)
To a solution of sodium hydride (100 mg, 3.0 mmol) and
3-(9-phenyl-9H-carbazol-3-yl)-9H-carbazole (816 mg, 2.0 mmol) in
dry DMF (40 mL) was stirred at room temperature for 1 h under argon
atmosphere. 2-Chloro-4,6-diphenyl-1,3,5-triazine (448 mg, 1.67
mmol) was added to the solution at room temperature, then refluxed
overnight. The mixture was poured into water and the precipitation
was collected by filtration and washed with water, methanol and DCM
to get 800 mg (75%) yellow solid.
Device Examples
All device examples were fabricated by high vacuum (<10.sup.-7
Torr) thermal evaporation. The anode electrode is 800 .ANG. of
indium tin oxide (ITO). The cathode consisted of 10 .ANG. of LiF
followed by 1000 .ANG. of Al. All devices were encapsulated with a
glass lid sealed with an epoxy resin in a nitrogen glove box (<1
ppm of H.sub.2O and O.sub.2) immediately after fabrication, and a
moisture getter was incorporated inside the package.
As used herein, the following compounds have the following
structures:
##STR00370##
Particular devices are provided. The organic stack of the Device
Examples 1 and 2 consisted of sequentially, from the ITO surface,
100 .ANG. of E1 as the hole injection layer (HIL), 300 .ANG. of
4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (.alpha.-NPD) as the
hole transporting layer (HTL), 300 .ANG. of host doped with E1 as
the emissive layer (EML), 100 .ANG. of H2 as the blocking layer
(BL), and 400 .ANG. of Alq as the electron transporting layer
(ETL).
Comparative Device Examples 1 and 2 were fabricated similarly to
Device Examples 1 and 2, except H3 was used as host.
Device structures for Device Examples 1 and 2 are provided in Table
2 and the corresponding measured device data is provided in Table
3.
TABLE-US-00002 TABLE 2 VTE PHOLEDs Example HIL HTL EML (doping %)
BL ETL Example 1 E1 NPD Compound 1 E1 5% H2 Alq Example 2 E1 NPD
Compound 1 E1 10% H2 Alq Comparative E1 NPD H3 E1 5% H2 Alq Example
1 Comparative E1 NPD H3 E1 10% H2 Alq Example 2
TABLE-US-00003 TABLE 3 VTE device data At 1000 nits At 40
mA/cm.sup.2 1931 CIE FWHM Voltage LE EQE PE L.sub.0 LT80% Example x
y .lamda..sub.max (nm) (V) (Cd/A) (%) (lm/W) (nits) (h) Example 1
0.324 0.623 520 66 5.7 40.6 11.3 22 2 12,769 86 Example 2 0.336
0.619 522 69 5.6 47.4 13.2 26.4 15,048 83 Comp. 0.316 0.628 520 64
5.7 45.5 12.7 25.1 12,635 46 Example 1 Comp. 0.317 0.630 520 64 5.2
54.4 15.1 32.6 16,264 29 Example 2
Device Examples 1 and 2 showed green PHOLEDs with Compound 1 as
host with different E1 doping concentrations. The comparative
examples used H3 (i.e., CBP, a commonly used PHOLED host) as the
host. As can be seen from the table, devices with Compound 1 as
host had comparative operating voltage, slightly lower efficiency
than devices with H3 as the host. However, the device operating
lifetime was much higher than comparative examples. Device Example
1 almost doubled the lifetime of Comparative Example 1 (86 h vs 46
h) and Device Example 2 almost tripled the lifetime of Comparative
Example 2 (83 h vs. 29 h). Therefore, Compound 1 is an excellent
host material for phosphorescent OLEDs.
It is understood that the various embodiments described herein are
by way of example only, and are not intended to limit the scope of
the invention. For example, many of the materials and structures
described herein may be substituted with other materials and
structures without deviating from the spirit of the invention. The
present invention as claimed may therefore includes variations from
the particular examples and preferred embodiments described herein,
as will be apparent to one of skill in the art. It is understood
that various theories as to why the invention works are not
intended to be limiting.
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